Enhancing Carrier Transport via σ‐Linkage Length Modulation in D‐σ‐A Semiconductors for Photocatalytic Oxidation

Abstract Carrier transport is an equally decisive factor as carrier separation for elevating photocatalytic efficiency. However, limited by indefinite structures and low crystallinities, studies on enhancing carrier transport of organic photocatalysts are still in their infancy. Here, we develop an σ‐linkage length modulation strategy to enhance carrier transport in imidazole‐alkyl‐perylene diimide (IMZ‐alkyl‐PDI, corresponding to D‐σ‐A) photocatalysts by controlling π–π stacking distance. Ethyl‐linkage can shorten π–π stacking distance (3.19 Å) the most among IMZ‐alkyl‐PDIs (where alkyl=none, ethyl, and n‐propyl) via minimizing steric hindrance between D and A moieties, which leads to the fastest carrier transport rates. Thereby, IMZ‐ethyl‐PDI exhibits remarkable enhancement in phenol degradation with 32‐fold higher rates than IMZ‐PDI, as well as the oxygen evolution rate (271‐fold increased). In microchannel reactors, IMZ‐ethyl‐PDI also presents 81.5 % phenol removal with high‐flux surface hydraulic loading (44.73 L m −2 h −1 ). Our findings provide a promising molecular design guideline for high‐performance photocatalysts and elucidate crucial internal carrier transport mechanisms.